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首页> 外文期刊>The journal of physical chemistry, A. Molecules, spectroscopy, kinetics, environment, & general theory >Probing the Photoionization Dynamics of 2-Cyclopenten-1-one via High-Resolution VUV-MATI Spectroscopy
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Probing the Photoionization Dynamics of 2-Cyclopenten-1-one via High-Resolution VUV-MATI Spectroscopy

机译：通过高分辨率Vuv-Mati光谱探测2-环戊中-1-1的光离子激励动力学

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摘要

2-Cyclopenten-1-one (2CP), which is a cyclic enone, has been considered an important precursor because of its versatile functionality in the synthesis of natural products and materials for biofuels. Here, we report the adiabatic ionization energy (AIE) and cationic structure of 2CP in the ionic transition between the neutral S-0 and the cationic D-0 states probed by high-resolution vacuum ultraviolet mass-analyzed threshold ionization (VUV-MATI) spectroscopy. From the 0-0 band position in the VUV-MATI spectrum supported by the VUV-photoionization efficiency curve, the AIE of 2CP was determined to be 9.3477 +/- 0.0004 eV (75,395 +/- 3 cm(-1)), which is in good agreement with the reference value but much more accurate. The measured MATI spectrum combined with the Franck-Condon fitting at the B3LYP/cc-pVTZ level revealed that the cationic structure of 2CP is twisted with the C-1 symmetry, whereas the neutral 2CP has the C-S symmetry. The results indicate that geometrical changes induced by ionization are mainly attributed to the electron removal from the highest occupied molecular orbital, which consists of nonbonding orbitals on the oxygen atom in the carbonyl group interacting with the sigma-orbitals in the molecular plane of 2CP. Consequently, lowering the C-1 symmetry for cationic 2CP led to the promotions of the ring-bending and ring-twisting modes in the MATI spectrum, which correspond to the ring puckering and C=C twisting in the S-0 state, respectively.
机译：2-环戊烯-1-酮（2CP）是一种环烯酮，因其在合成天然产物和生物燃料材料中的多功能性而被认为是一种重要的前体。本文报道了用高分辨真空紫外质量分析阈值电离（VUV-MATI）光谱探测的中性S-0态和阳离子D-0态离子跃迁中2CP的绝热电离能（AIE）和阳离子结构。根据VUV光电离效率曲线支持的VUV-MATI光谱中的0-0波段位置，确定2CP的AIE为9.3477+/-0.0004 eV（75395+/-3 cm（-1）），这与参考值非常一致，但更准确。在B3LYP/cc pVTZ水平上，测量的MATI谱与Franck-Condon拟合相结合，表明2CP的阳离子结构是扭曲的，具有C-1对称性，而中性2CP具有C-S对称性。结果表明，电离引起的几何变化主要归因于电子从最高占据分子轨道上的移除，该轨道由羰基氧原子上的非键轨道组成，与2CP分子平面上的sigma轨道相互作用。因此，降低阳离子2CP的C-1对称性导致MATI光谱中的环弯曲和环扭转模式的提升，这分别对应于S-0状态下的环皱折和C=C扭转。

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